Anthrachrysone derivatives.



THE-MAIN, eeeniu to us I BRBNING, OF HQCHS'f-ON--l.lilE--ILilN, GERMAN Ti, A CORPORATION OF GERMANY Wur t-w? "I "L. All

ANUJOSEF ERBER, OF' HoCHsT-ON- miteultuuh, VORM. MEISTER, LUGIUS &

Pas"

AN TEiYTELEEBX "SONE DEEP] ATIVES No. sneer.

Specification of l.

11ers Potent.

Patented Nov. 19, ieor.

Application filed November 27, 1305- S- risl No. 345.413- (Specimens) To all who c it may COTLCfi'ii-L:

Be it known that we, 13.1mm .t-loitomci,

Ph. D. uni-i Josnr Eunhn Ph. D. chemists citizens otthe Empire of Germany, and residing at Franltl'ort-onthe-r\fhun, end

- llochst-on the Main, Germany, respecthrachrysone with 2 molecular proportions of formaldehyde in alkaline solution a, new product may be obtained which when treat ed with ammonia or with aliphatic or are matic a-inins yield u series of peculiorhew nitrogenous derivatives of the zuithrmpiinoue series. For their production it is, however,

not absolutely necessary to isolate the product of the reaction of formaldehyde on onthrechrysone and to treat it with an oniin in \atseperatc operation. 011 the contrary, both reactions may be combined in a. single operation by causing formaldehyde to dot under certain conditions on :inthrechrysone inpresencc oi {LII umin. Yet a. third method is applicable in some cases, namely combining an aliphatic or aromatic umin with forma-ldehyde and allowing the product to act under suitable conditions on zinthruchrysone.

Jib-ample I rysone- 110 kilos of zmtlu'uchrysonc and kilos of caustic soda are dissolved with old of heat in 1200 liters of water; the solution. filtered ll necessary and cooled to from BO-25 C,

whereupon kilos of commercial formeldc dried, I The product thus obtained is almost,

insoluble in water, ligroine ether, hardly Jll'anufizcztra of thclpmduci of reaction ojifomuzldchyde on on tit-m1;

soluble in alcohol an chloroform, very little sohible in acetone; it dissolves in dilute caustic alkali lycs to on orungcycllow solution in concentrated sulfuric acid to a, red solution. The reaction takes place according to the following equation;

Erample II-Rcaeii0n ofcmins on the product obtained by the reaction 0ff01maZde--.

li-yde on (Lftfltl"d6h7" lj8()7l5=--I1l a closed vessel 100 kilos of the product of the reaction of formaldehyde on lmthrachrysone, obtained for instance, as described above, are heated to ebullition with a quantity of onilin'in excess of the qmintity ol the reuctiolvproduct; dissolution ()CC-UIS, and a mixture of a nilin uud water disl'ils. of water has ceased, the heutin is intere rupted and the solution allowed to cool, whereupon port of the nitrogenous anthraquiuone product separates as crystals, the rest being obtained by distilling the anilin with stomiu. crystals of basic and acid character. They dissolve in dilute mineral acids to a yellow, in dilute cunt-die ullculics to an orange solution. The new product is little soluble in the solvents before mentioned; it cannotbe i used without decomposing and cannotbe subliined;

rinnlogous nitrogenous anthmquinone derivatives have been obtained by substituting For the anilin employed in the preceding example the following ainins:-nmn10nia,

nicthylmnin, ethylamin, dimethylamin, di-- nilin. All compounds thusobtained coincide As soon as the formation,

completely in,theirche1 nicaland very closely The crude product remaining is dissolved in In their physical behavior. l dilute hydrochloric acid, the solution filtered OH l A and the nitrogenous product precipitated in OEFOH, V 00 on a purified state by adding lrsli carbonate. It is identical with the pro uctiobtained acll cording to Example II if ortho-toluidin is 1 used. For the ortho-tol'uidin in this exam- OH ,ple may be substituted-one of the primary or A os co l OH OH "s 0 U I I a. on l l FMCHQOWL'AF wherein A means an amin. C0 OIH I Example I II. Manufacture of nitroge- OH nous anfltmgm none derwat'ioes by the simnlta- H-C (i rgaousi'bactzon of formaldehyde and amin on on- 1 l I t m0 rysona-A mixture of 55 kilos ofanthraqluinone, 350 kilos 0i dnnethylanihn, OH i 6 1000 (110s of alcohol of 96per'cent strength u v wherein A means an amin and and kilos of forma'ldeh *de of 40' er cent strength is heated in an aijpamtus Ming, a (OH,O A) represents the compound formed reflux condenser on the water-bath untilall by lamm with foi'malde'h f a pears clearly dissolved. The'alcohol is -i,1ntheEXampl9 I and IV',]dent1c.a1 t en distilled oil'and the excess of di1nethyl- Products are i d the m m anilin is expelled with steam. The crude is used product remaining is dissolved in dilute, h v L drochloric -achland the solution is filtere d ter'hgmmei etherzhai'dly Slub]e.m'alc0h0l v a d theipi g product precipitated in r and chloroform, very little soluhle in acetone. a urified state by adding sodium carbonate. new products are used In the a condensation product of facture of anthracene-dyestulis. Although s eoific example-s ot the menu facturc and o the ainins to he used therein have been givenabov'e, itis to be understood that the .inven V amples nor to the proportions mentioned therein, and that for theamins cited others may be substituted either aloneor mixed.

l-l aving now We claim is 1 I 1. T he process herein described of making T e product thus obtained is identical with that obtained according to Example II if dlmethylanilin is used therein. For the di methylanilin in this example may he sub stituted one of the amine mcnziomd in EX- ampleII.

' which consists in causing formaldehyde and an amin to act on anthrachrysone,it being immaterial in which order the three bodies are brought-together. 2. As new product, a nitrogenous derive; tive of anthraquinone, obtained by the interaction of anthrachrvsone, formaldehyde and wherein A means an amin.

Example I V zllztnnfaeturc of nitrogenous anti'zmqninonc. derivatives fry the action of a forntcidchy dc with a primary or secondary mn'in on (tnfiz'mchry s0ne.-500 kilos of ortho-toluidin are heated on the Water-bath with 4:5 kilos of formaldenumeral acids to a yellow solution. hyde-of 40 per cent strength until anhydro- I In testimony, that we-claiin theioregoing fornialdehyd'e-ortho toluidin is, produced. f as our invention, we have signed our "names There are then added kilos of a'nthrachryl in p rcscnce of two subscribing witnesses. sone. and 500 kilos of alcohol of 96 per cont 1 BENNO HOMOLKA.

tallinc powder, insoluble in Water, hardly soluble in the usu hle Without ('lecoinposition and dissolving n dilute caustic alkalies to an orange, in' dilute strength and the whole is heated for some JOSE Ii ERBER. hours in a reflux apparatus on the watcr-- athj The alcohol is then distilled and the i excess of ortho-toluidin expelled with. steam. i

Wit posses.

JEAN Grimm, CARL G mm 1..

secondary amins mentioned in Example IL,

The products obtained are insoluble wa-' nitrogenous derivatives of antliraquinone.

al organic solvents; not fusition is not limited to the, 6x

described "our invention, what I an amin, said product being an orange crys- A 

